The spin-orbit interaction couples the electrons' motion to their spin. Accordingly, passing a current in a material with strong spin-orbit coupling generates a transverse spin current (spin Hall effect, SHE) and vice-versa (inverse spin Hall effect, ISHE) 1-3 . The emergence of SHE and ISHE as charge-to-spin interconversion mechanisms offers a variety of novel spintronics functionalities 4,5 and devices, some of which do not require any ferromagnetic material 6 . However, the interconversion efficiency of SHE and ISHE (spin Hall angle) is a bulk property that rarely exceeds ten percent, and does not take advantage of interfacial and low-dimensional effects otherwise ubiquitous in spintronics hetero-and mesostructures. Here, we make use of an interface-driven spin-orbit coupling mechanism  the Rashba effect 7  in the oxide two-dimensional electron system (2DES) LaAlO3/SrTiO3 to achieve spin-to-charge conversion with unprecedented efficiency. Through spin-pumping, we inject a spin current from a NiFe film into the oxide 2DES and detect the resulting charge current, which can be strongly modulated by a gate voltage. We discuss the amplitude of the effect and its gate dependence on the basis of the electronic structure of the 2DES. Perovskite oxide materials possess a broad range of functionalities, some of which can be very appealing for spintronics. This includes half-metallicity in mixed-valence manganites  that can be used to produce giant tunnel magnetoresistance 8  or multiferroicity  through which magnetization direction can be electrically controlled at low power 9 . The recent years have seen the emergence of novel spintronics effects based on the generation and control of pure spin currents through spin-orbit effects in semiconducting and metallic systems 1-3 . However, despite a renewal of interest for 4d and 5d transition metal perovksites 10 , spin-orbit effects remained largely unexplored in oxide spintronics.An emerging direction in oxide research aims at discovering novel electronic phases at interfaces between two oxide materials 11 . A well-known example is the LaAlO3/SrTiO3 system: while both LaAlO3 (LAO) and SrTiO3 (STO) are wide bandgap semiconductors, a high-mobility two-dimensional electron system (2DES) forms at their interface 12 if the LAO thickness is at least 4 unit-cells (uc). Interestingly, LAO/STO possesses several remarkable extra functionalities including a gate-tuneable Rashba effect 13,14 , which makes it particularly appealing for spintronics.The Rashba effect is a manifestation of the spin-orbit interaction (SOI) in solids, where spin degeneracy associated with the spatial inversion symmetry is lifted due to a symmetry-breaking electric field normal to an heterointerface 15 . In a Rashba 2DES, the flow of a charge current results in the creation of a nonzero spin accumulation 16,17 coming from uncompensated spin-textured Fermi surfaces. Recently, the converse effect so-called inverse Edelstein effect (IEE)  that is a spin-to-charge conversion through SOI  was discovered a...

The nitroxide-containing nucleoside Çm is reported as the first rigid spin label for paramagnetic modification of RNA by solid-phase synthesis. The spin label is well accommodated in several RNA secondary structures as judged by its minor effect on the thermodynamic stability of hairpin and duplex RNA. Electron paramagnetic resonance (EPR) spectroscopic characterization of mono-, bi-, and trimolecular RNA structures shows that Çm will be applicable for advanced EPR studies to elucidate structural and dynamic aspects of folded RNA.

The ability of RNA to interconvert between multiple conformational states is essential for the diversity of biological functions that have been discovered in the recent past. [1] For example, the correct operation of regulatory RNA elements, such as riboswitches, is based on the precise interplay of alternative RNA conformations.[2] Studying the molecular mechanisms of RNA function entails probing RNA-folding intermediates on the energy landscape. EPR spectroscopy, in particular, has been increasingly applied to obtain structural information on nucleic acids, including local conformational changes in RNA [3] and the identification of metal-ion binding sites.[4] Pulsed EPR techniques (PELDOR/ DEER) have been used to determine distances between paramagnetic centers in specifically modified RNA. [5] PELDOR should therefore be suitable for the detection of alternative RNA conformations that involve distinct changes in base-pairing patterns.The accessibility of spin-labeled RNA still poses the major challenge for the widespread applicability of powerful EPR techniques. Nitroxide radicals are the most commonly used type of paramagnetic labels for nucleic acids. Several methods have been reported for attaching nitroxide groups at internal positions at the ribose, the phosphate backbone, or at nucleobases, often by means of multiatom linkers that provide several unwanted degrees of rotational freedom.[6] Rigid nitroxide spin labels conjugated to the nucleobase or to nucleobase analogues have been reported for DNA.[7] Our RNA spin-labeling approach addresses the direct attachment of nitroxide labels onto RNA nucleobases, such that conformational changes can be directly detected by PELDOR (i.e., by the change in distance between two labeled nucleotides). The nucleobase spin labels used in this study are also designed to preserve the Watson-Crick base-pairing capability of labeled nucleotides and not to interfere with alternative base-pairing patterns in different RNA conformations.Here, we describe the installation of nitroxide spin labels on exocyclic amino groups of the RNA nucleobases guanine, adenine, and cytosine (Figure 1) with unprecedented efficiency, and we report on the evaluation of RNA secondary structures by pulsed double electron resonance spectroscopy.The convertible nucleosides [8] O 4 -(4-chlorophenyl)uridine, O 6 -(4-chlorophenyl)inosine, and 2-fluoroinosine were incorporated into RNA by solid-phase synthesis using commercially available, modified 2'-O-tert-butyldimethylsilylprotected building blocks 1-3 in combination with standard RNA 2'-O-triisopropylsilyloxymethyl-protected nucleoside phosphoramidites. In a postsynthetic modification step, the 4-chlorophenyl or fluoride leaving groups were displaced by

The radical S-adenosyl-L-methionine tryptophan lyase NosL converts L-tryptophan into 3-methylindolic acid, which is a precursor in the synthesis of the thiopeptide antibiotic nosiheptide. Using electron paramagnetic resonance spectroscopy and multiple L-tryptophan isotopologues, we trapped and characterized radical intermediates that indicate a carboxyl fragment migration mechanism for NosL. This is in contrast to a proposed fragmentation-recombination mechanism that implied Cα-Cβ bond cleavage of L-tryptophan. Although NosL resembles related tyrosine lyases, subtle substrate motions in its active site are responsible for a fine-tuned radical chemistry, which selects the Cα-C bond for disruption. This mechanism highlights evolutionary adaptation to structural constraints in proteins as a route to alternative enzyme function.